JP2011079900A - Sheet with film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To allow formation of a film which is excellent in hardness, transparency, rub resistance, chemical resistance, resistance to staining, and heat resistance, allows maintenance of surface gloss even if a polishing operation is not frequently performed, and has sufficient perceptibility and strength for bearing long-term use, in a sheet with a film, to which ultraviolet curable paint is applied. <P>SOLUTION: The ultraviolet curable paint 1, in which at least one compound of an isocyanate compound 2 and a hydroxy compound 3 contains an unsaturated urethane compound having an unsaturated bond, contains 0.5-3 wt.% of an antistatic agent 5, 0.5-3 wt.% of a silver complex-based antibacterial agent 6, and 0.5-3 wt.% of an unsaturated polyester resin 7 in 100 wt.%. The sheet 10 with a film is obtained by applying it to a transparent organic synthetic resin sheet so that its application thickness is within 8 μm ±1 μm to perform UV curing, and has excellent abrasion resistance, chemical resistance, resistance to ultraviolet radiation, transparency, antibacterial property, and noninflammability. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention applies an ultraviolet curable coating to form a coating film having excellent hardness, transparency, friction resistance, chemical resistance, stain resistance, heat resistance, and strength that can withstand long-term use. The present invention relates to a sheet with a film.

  Conventionally, flooring materials used in stores, hospitals, factories, etc. are mainly organic synthetic resin sheets such as vinyl chloride, wood materials such as flooring, ceramic materials such as porcelain tiles, stone materials such as marble, etc. Further, a polishing agent such as wax or floor polish is applied for the purpose of imparting high gloss to the surface of these floor materials, improving durability, and preventing slippage.

  However, since floors of stores, hospitals, factories, etc. are very many people walking, just applying a conventional polish such as wax or floor polish will take a few days to a week after construction. It is necessary to repeat the work of peeling off the coating film and applying the polishing agent again in a short period of time, since the surface gloss of the floor surface is significantly reduced and scratches and colored stains become conspicuous. There was a problem that there was.

  Therefore, in order to solve such a problem, Patent Document 1 discloses a paint containing at least one unsaturated urethane compound using at least one isocyanate compound having an unsaturated bond and a hydroxyl compound as a raw material, and having a polyalkyleneoxy group. An invention of a floor paint having a content of 2 to 16% by weight and a ratio of the number of unsaturated bonds of 6 or more and a paint coating thereof is disclosed. This makes it possible to form a coating film that is excellent in stain resistance and gloss retention, can easily remove scratches and colored stains, and can use water as a solvent, and its paint coating It is going to be a thing.

JP 2002-069371 A

  However, in the technique described in Patent Document 1, since the hardness and friction resistance of the coating material using the floor coating are relatively low, the coating material is easily scratched, and the chemical resistance of the coating material is low. In order to maintain the gloss of the floor, the floor must be polished many times, and the paint coating is not sufficiently transparent. In the case of printing, there is a problem that the visibility is insufficient.

  Therefore, the present invention has been made to solve such problems, and is excellent in hardness, transparency, friction resistance, chemical resistance, contamination resistance, and heat resistance, and is frequently polished. The object of the present invention is to provide a sheet with a coating film on which a coating film having a sufficient visibility and strength enough to withstand long-term use can be maintained even if it is not present.

  The sheet with a coating film according to the invention of claim 1 contains an unsaturated urethane compound having an isocyanate compound and a hydroxy compound as raw material compounds, and at least one of the raw material compounds has an unsaturated bond. Is a sheet with a coating film formed by applying an ultraviolet curable paint containing a transparent organic synthetic resin sheet, wherein the ultraviolet curable paint has at least one of the unsaturated urethane compounds having a polyalkyleneoxy group. And the content of the polyalkyleneoxy group is in the range of 2 to 16% by weight with respect to the total amount of the isocyanate compound and the hydroxy compound used in the unsaturated urethane compound, The total number of moles of raw materials having saturated bonds, and the number of unsaturated bonds in the number of moles of raw materials having unsaturated bonds. The value obtained by dividing the sum of the product multiplied by the number of isocyanate groups of the isocyanate compound is in the range of 6 to 9, or the total sum of the number of moles of the raw material having an unsaturated bond. The value obtained by dividing the sum of the number of moles of the unsaturated bond by the number of unsaturated bonds and the sum of the number of hydroxyl groups of the hydroxy compound is within the range of 6-9. In 100% by weight of the ultraviolet curable paint, an antistatic agent in the range of 0.5% by weight to 3% by weight, a silver complex antibacterial agent in the range of 0.5% by weight to 3% by weight, and 0 An ultraviolet curable paint containing 5% to 3% by weight of an unsaturated polyester resin, and the transparent organic synthetic resin sheet is used in a clean room superior in class 1000 or more. Coating thickness within the range of 8μm ± 1μm It is applied and cured with UV to form a coating film, and the surface of the transparent organic synthetic resin sheet is subjected to an easy adhesion treatment, and the coating film visibility (visible light transmittance) Is 90% or more.

  Here, “the total amount of the isocyanate compound and the hydroxy compound used in the unsaturated urethane compound” means all the materials used for producing an ultraviolet curable paint regardless of the presence or absence of a polyalkyleneoxy group. The total amount of isocyanate compound and hydroxy compound.

  Further, “the content of the polyalkyleneoxy group” will be specifically described. In order to produce an ultraviolet curable paint, A1 gram of isocyanate compound A, B1 gram of isocyanate compound B, C1 gram of hydroxy compound C, hydroxy Assuming that D1 grams of compound D is used, isocyanate compound A contains 2% by weight of polyalkyleneoxy groups in the molecule, and hydroxy compound C contains 2% by weight of polyalkyleneoxy groups in the molecule. When compound D does not contain a polyalkyleneoxy group, the content of polyalkyleneoxy group: W (% by weight) is represented by the following formula (1).

  Furthermore, “the value obtained by dividing the sum of the number of moles of the raw material having unsaturated bonds by the number of moles of the raw material having unsaturated bonds multiplied by the number of unsaturated bonds” Explaining that the amount of unsaturated compound A having an unsaturated bond is A3 mol (mol), the number of unsaturated bonds is A4, and the amount of isocyanate compound B having an unsaturated bond is B3 mol (mol) is an unsaturated bond. The number of B4 hydroxy compound C having an unsaturated bond is C3 mol (mol), the number of unsaturated bonds is C4, and the amount of hydroxy compound D having an unsaturated bond is D3 mol (mol). When the number of saturated bonds is D4, a value obtained by dividing the sum of the number of moles of the raw material having unsaturated bonds by the sum of the number of moles of the raw material having unsaturated bonds multiplied by the number of unsaturated bonds: X is represented by the following formula (2). It is.

  Further, “the number of isocyanate groups of the isocyanate compound” will be specifically described. When the number of isocyanate groups of the isocyanate compound A is A5 and the number of isocyanate groups of the isocyanate compound B is B5, the number of isocyanate groups of the isocyanate compound. : Y is represented by the following formula (3).

  Further, “the number of hydroxyl groups of the hydroxy compound” will be specifically described. When the number of hydroxyl groups of the hydroxy compound C is C5 and the number of hydroxyl groups of the hydroxy compound D is D5, the number of hydroxyl groups of the hydroxy compound: Z is It is represented by Formula (4).

  Here, as the antistatic agent, “Pelestat” manufactured by Sanyo Kasei Kogyo Co., Ltd., an antistatic agent for polyester resin, etc. are used, and as the silver complex antibacterial agent, a thiosulfite silver complex or the like is used. Can do. Furthermore, as "transparent organic synthetic resin sheet", PE (polyethylene) sheet, PP (polypropylene) sheet, PET (polyethylene terephthalate) sheet, acrylic resin (including methacrylic resin) sheet, vinyl chloride sheet, polyurethane sheet, etc. Can be used.

  Furthermore, “easy adhesion treatment” refers to a treatment in which a transparent organic synthetic resin sheet has improved adhesion to other sheets, films, paints or adhesives. For example, a transparent organic synthetic resin sheet There are methods such as coating the surface with a polyurethane layer.

  In the sheet with a coating film according to the invention of claim 2, a transparent organic synthetic resin sheet is pasted on the surface of a printed sheet printed on the surface, and an isocyanate compound and a hydroxy compound are placed on the transparent organic synthetic resin sheet. A sheet with a coating film formed by applying an ultraviolet curable coating material containing an unsaturated urethane compound as a raw material compound, wherein at least one of the raw material compounds contains an unsaturated urethane compound having an unsaturated bond, In the ultraviolet curable paint, at least one of the unsaturated urethane compounds has a polyalkyleneoxy group, and the content of the polyalkyleneoxy group is the isocyanate compound used for the unsaturated urethane compound and the hydroxy The raw material having an unsaturated bond is in the range of 2 to 16% by weight based on the total amount of the compound. The value obtained by multiplying the value of the sum of the number of moles of the raw material having the unsaturated bond by the sum of the number of moles of the unsaturated bond multiplied by the number of unsaturated bonds and the number of isocyanate groups of the isocyanate compound. The sum of the number of moles of the raw material having an unsaturated bond within the range of 6 to 9 or the product of the number of moles of the raw material having an unsaturated bond multiplied by the number of unsaturated bonds is divided. The value obtained by multiplying the obtained value by the number of hydroxyl groups of the hydroxy compound is in the range of 6 to 9, and the charge in the range of 0.5 to 3% by weight in 100% by weight of the ultraviolet curable paint. An ultraviolet curable paint containing an inhibitor, a silver complex antibacterial agent in the range of 0.5 wt% to 3 wt%, and an unsaturated polyester resin in the range of 0.5 wt% to 3 wt% Yes, this UV-curable coating material has a clean loop excellent in class 1000 or higher. The surface of the transparent organic synthetic resin sheet is formed by coating the transparent organic synthetic resin sheet on the transparent organic synthetic resin sheet so that the coating thickness is within a range of 8 μm ± 1 μm and curing with ultraviolet rays. Is subjected to easy adhesion treatment, and the coating film has a visibility (visible light transmittance) of 90% or more.

  The sheet with a coating film according to a third aspect of the present invention is the structure of the first or second aspect, wherein the surface smoothness of the coating film is an optical level of smoothness. Here, “optical level smoothness” refers to a level of smoothness in which a mirror image is not distorted at all even when a transparent coated sheet is attached to the mirror surface.

  The sheet with a coating film according to the invention of claim 4 is the structure according to any one of claims 1 to 3, wherein the transparent synthetic organic resin sheet has a thickness in the range of 25 μm to 200 μm, more preferably. It is a PET (polyethylene terephthalate) sheet in the range of 50 μm to 100 μm.

  The sheet with a coating film according to a fifth aspect of the present invention is the sheet according to any one of the first to fourth aspects, wherein the antistatic agent comprises an antistatic agent for a polyester resin. Here, as an antistatic agent for polyester resin, a mixture of polyglycerin fatty acid ester and calcium silicate can be used.

  The sheet with a coating film according to a sixth aspect of the present invention is the sheet according to any one of the first to fifth aspects, wherein the silver complex antibacterial agent comprises a thiosulfite silver complex. Here, the silver thiosulfite complex can be obtained, for example, by dissolving silver acetate in pure water at 40 ° C. to form a saturated solution, and sequentially dissolving sodium sulfite and sodium thiosulfate in this saturated solution.

  The sheet with a coating film according to the invention of claim 1 contains an unsaturated urethane compound having an isocyanate compound and a hydroxy compound as raw material compounds, and at least one of the raw material compounds has an unsaturated urethane compound having an unsaturated bond. It is a sheet with a coating film formed by applying an ultraviolet curable paint containing on a transparent organic synthetic resin sheet, and the ultraviolet curable paint has at least one unsaturated urethane compound having a polyalkyleneoxy group, The content of polyalkyleneoxy group is in the range of 2 to 16% by weight with respect to the total amount of isocyanate compound and hydroxy compound used in the unsaturated urethane compound, and the number of moles of raw material having an unsaturated bond Is the sum of the values obtained by multiplying the number of moles of raw materials having unsaturated bonds by the number of unsaturated bonds, and dividing the sum by The value obtained by multiplying the number of isocyanato groups of the socyanate compound is in the range of 6 to 9, or the total number of moles of raw materials having unsaturated bonds, and the number of moles of raw materials having unsaturated bonds is unsaturated bond. The value obtained by multiplying the sum of the number and the number of hydroxyl groups of the hydroxy compound is in the range of 6-9, and in 100% by weight of the ultraviolet curable paint, 0.5% by weight An antistatic agent in the range of 3 wt%, a silver complex antibacterial agent in the range of 0.5 wt% to 3 wt%, and an unsaturated polyester resin in the range of 0.5 wt% to 3 wt% UV curable paint containing UV and applied to a transparent organic synthetic resin sheet in a clean room superior in class 1000 so that the coating thickness is within the range of 8 μm ± 1 μm. UV-cured to form a coating film. Viewing rate (visible light transmittance) of 90% or more.

  The sheet with a coating film according to the present invention contains an unsaturated urethane compound using an isocyanate compound and a hydroxy compound as raw materials, and at least one of the raw material compounds contains an unsaturated urethane compound having an unsaturated bond. Since it is formed by applying a curable coating, it has excellent chemical resistance, stain resistance, and heat resistance. Here, when the content of the polyalkyleneoxy group: W (% by weight) is in the range of 2% by weight to 16% by weight, the coating film formed by applying an ultraviolet curable coating and curing it with ultraviolet rays is warped. The coating film is excellent in stain resistance and gloss retention performance without causing cracks or cracks. When W is less than 2% by weight, the coating film may be warped or cracked. When W is more than 16% by weight, the stain resistance and gloss retention performance of the coating film are deteriorated.

  Further, the value of the sum of the number of moles of raw materials having unsaturated bonds, the sum of the number of moles of raw materials having unsaturated bonds multiplied by the number of unsaturated bonds, divided by X: isocyanato of the isocyanate compound The number of groups: Y multiplied by X · Y, or X multiplied by the number of hydroxyl groups of the hydroxy compound: Z, that is, either X · Z has a value in the range of 6-9. Needed. When both X · Y and X · Z are less than 6, the stain resistance and gloss retention performance of the coating film become insufficient, and the coating film is likely to be colored and scratched. Moreover, when all of X * Y and X * Z exceed 9, it will become easy to warp in a coating film or to reduce the adhesiveness of a coating film.

  Furthermore, since the silver complex antibacterial agent is contained within the range of 0.5 wt% to 3 wt%, the coating film can have an antibacterial function, and the coating film surface is always kept clean. Contamination can be prevented. Moreover, since the unsaturated polyester resin is contained in the range of 0.5 wt% to 3 wt%, the hardness of the coating film is remarkably improved by being protected by the high hardness unsaturated polyester resin.

  The present inventor has conducted extensive experimental research on the relationship between the coating thickness of the ultraviolet curable coating and the coating film performance. As a result, the coating thickness is within the range of 8 μm ± 1 μm on the transparent organic synthetic resin sheet. It was found that the hardness, transparency, and friction resistance of the coating film were remarkably improved by applying the coating and curing with UV to form a coating film, and the present invention was completed based on this finding. It is. That is, when the coating thickness is 8 μm, the most excellent hardness, transparency, and friction resistance can be obtained, and the coating thickness needs to be within the range of 8 μm ± 1 μm, and further 8 μm ± 0. More preferably, it is within the range of 5 μm.

  Furthermore, since the coating, drying, and UV curing processes are performed in a clean room that is superior to class 1000 or higher, the surface smoothness, transparency, and antifouling properties do not deteriorate because dust does not enter the coating film. Since it is applied on a transparent organic synthetic resin sheet whose surface has been subjected to an easy adhesion treatment, the coating film has excellent adhesion. Moreover, since the visibility (visible light transmittance) of the coating film is 90% or more, even if the visibility (visible light transmittance) of the transparent organic synthetic resin sheet is 90% or more, the sheet with the coating film As a result, a sheet with a coating film excellent in transparency can be obtained.

  In this way, it is excellent in hardness, transparency, friction resistance, chemical resistance, stain resistance, and heat resistance, and can maintain the gloss of the surface without frequent polishing work. It becomes a sheet | seat with a coating film in which the coating film which has the intensity | strength which can endure visibility and long-term use was formed.

  The sheet with a coating film according to the invention of claim 2 is obtained by attaching a transparent organic synthetic resin sheet on the surface of a printed sheet printed on the surface, and using an isocyanate compound and a hydroxy compound as raw materials on the transparent organic synthetic resin sheet An ultraviolet curable coating material containing an unsaturated urethane compound as a compound and containing an unsaturated urethane compound in which at least one of the raw material compounds has an unsaturated bond is applied.

  Here, the ultraviolet curable coating material is an isocyanate compound in which at least one of the unsaturated urethane compounds has a polyalkyleneoxy group, and the content of the polyalkyleneoxy group: W (% by weight) is used for the unsaturated urethane compound. In addition, the coating film formed by applying an ultraviolet curable coating material and curing it with ultraviolet rays does not cause warping or cracking. It becomes a coating film excellent in stain resistance and gloss retention performance. If W is less than 2% by weight, the coating film may be warped or cracked. If W is more than 16% by weight, the stain resistance and gloss retention performance of the coating film are reduced.

  Further, the value of the sum of the number of moles of raw materials having unsaturated bonds, the sum of the number of moles of raw materials having unsaturated bonds multiplied by the number of unsaturated bonds, divided by X: isocyanato of the isocyanate compound The number of groups: Y multiplied by X · Y, or X multiplied by the number of hydroxyl groups of the hydroxy compound: Z, that is, either X · Z has a value in the range of 6-9. Needed. When both X · Y and X · Z are less than 6, the stain resistance and gloss retention performance of the coating film become insufficient, and the coating film is likely to be colored and scratched. Moreover, when all of X * Y and X * Z exceed 9, it will become easy to warp in a coating film or to reduce the adhesiveness of a coating film.

  Furthermore, since the silver complex antibacterial agent is contained within the range of 0.5 wt% to 3 wt%, the coating film can have an antibacterial function, and the coating film surface is always kept clean. Contamination can be prevented. Moreover, since the unsaturated polyester resin is contained in the range of 0.5 wt% to 3 wt%, the hardness of the coating film is remarkably improved by being protected by the high hardness unsaturated polyester resin.

  The present inventor has conducted extensive experimental research on the relationship between the coating thickness of the ultraviolet curable coating and the coating film performance. As a result, the coating thickness is within the range of 8 μm ± 1 μm on the transparent organic synthetic resin sheet. It was found that the hardness, transparency, and friction resistance of the coating film were remarkably improved by applying the coating and curing with UV to form a coating film, and the present invention was completed based on this finding. It is. That is, when the coating thickness is 8 μm, the most excellent hardness, transparency, and friction resistance can be obtained, and the coating thickness needs to be within the range of 8 μm ± 1 μm, and further 8 μm ± 0. More preferably, it is within the range of 5 μm.

  In addition, UV curable paint is applied on a transparent organic synthetic resin sheet that has been subjected to easy adhesion treatment in a clean room of class 1000 or higher, dried and UV cured. Since dust does not enter the surface, the surface smoothness, transparency and antifouling properties are not lowered, and the adhesion of the coating film is extremely excellent.

  Furthermore, since the visibility (visible light transmittance) of the coating film is 90% or more, even if the visibility (visible light transmittance) of the transparent organic synthetic resin sheet is 90% or more, the coated sheet In this case, the printing applied to the surface of the printing sheet can be clearly seen through the transparent organic synthetic resin sheet and the coating film without decreasing transparency, as if it were a transparent organic synthetic resin sheet And it will look good as if no coating was present. Thus, it becomes a sheet | seat with a coating film very excellent in the visibility of a printing sheet.

  In this way, it is excellent in hardness, transparency, friction resistance, chemical resistance, stain resistance, and heat resistance, and can maintain the gloss of the surface without frequent polishing work. It becomes a sheet | seat with a coating film in which the coating film which has the intensity | strength which can endure visibility and long-term use was formed.

  In the sheet with a coating film according to the invention of claim 3, the surface smoothness of the coating film is an optical level of smoothness. When a transparent coating film is formed on a conventional transparent organic synthetic resin sheet, the surface smoothness of the coating film is poor, and the mirror image is distorted when pasted on the mirror surface. However, the sheet with a coating film according to the present invention has an optical surface smoothness of the coating film, and the mirror image is not distorted at all even when applied to the mirror surface. Alternatively, in addition to the effect of the invention according to claim 2, the surface smoothness of the sheet with the coating film becomes extremely excellent, and the appearance of printing applied to the floor surface or the surface of the printing sheet to be applied more reliably is impaired. In addition, the coated sheet is excellent in scratch resistance and stain resistance.

  In the sheet with a coating film according to the invention of claim 4, the transparent organic synthetic resin sheet is a PET (polyethylene terephthalate) sheet having a thickness in the range of 25 μm to 200 μm. In addition to the effect of the invention according to any one of the above, the sheet manufacturing cost can be reduced and the sheet with a coating film having appropriate strength and appropriate flexibility can be obtained. As an advertising sheet, construction work such as sticking to a floor or a wall becomes easy, and the handling is excellent.

  In the sheet with a coating film according to the invention of claim 5, since the antistatic agent is an antistatic agent for polyester resin, in addition to the effect of the invention according to any one of claims 1 to 4, UV curable paint containing unsaturated polyester resin has good compatibility with unsaturated polyester resin, can more reliably prevent dust from adhering to the surface of the coating as an antistatic agent, and more reliably with scratch resistance It can be set as the sheet | seat with a coating film excellent in property and stain resistance.

  In the ultraviolet curable paint according to the invention of claim 6, since the silver complex antibacterial agent is composed of a thiosulfite silver complex, in addition to the effect of any one of claims 1 to 5, It has a superior deterrent effect against microorganisms and viruses, has good compatibility with unsaturated urethane compounds, can exhibit antibacterial action more reliably, and forms a coating film with excellent stain resistance Can do.

FIG. 1 is a flowchart showing a method for producing a coated sheet according to Example 1 of the present invention. FIG. 2 is a perspective view showing the structure of the coated sheet according to Example 1 of the present invention. FIG. 3 is a perspective view showing a sheet with a coating film according to a first application example of Example 1 of the present invention. FIG. 4 is a perspective view showing a coated sheet according to a second application example of Example 1 of the present invention. FIG. 5 is a perspective view showing a structure of a sheet with a coating film according to Example 2 of the present invention. FIG. 6 is a perspective view showing a coated sheet according to a first application example of Example 2 of the present invention. FIG. 7: is a perspective view which shows the sheet | seat with a coating film concerning the 2nd application example of Example 2 of this invention.

  In order to carry out the present invention, as a paint for forming a coating film of a sheet with a coating film, an unsaturated urethane compound containing an isocyanate compound and a hydroxy compound as a raw material compound is contained, and at least one compound among the raw material compounds It is necessary to use an ultraviolet curable paint containing an unsaturated urethane compound having an unsaturated bond. Here, the unsaturated bond is preferably present in the hydroxy compound. Below, the manufacturing method of the unsaturated urethane compound obtained by a urethanation reaction with an isocyanate compound and the hydroxy compound which has an unsaturated bond originating in an acryloyl group or a methacryloyl group in a molecule | numerator is demonstrated.

  Here, as the isocyanate compound, a monoisocyanate compound, a diisocyanate compound, a polyisocyanate compound, and the like can be used, and a polyisocyanate compound is particularly preferable. Examples of the polyisocyanate compound include an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and an aromatic polyisocyanate compound, and an aliphatic polyisocyanate compound is particularly preferable. Among them, those having 3 or more isocyanato groups are preferable.

  As the aliphatic polyisocyanate compound, those mainly composed of saturated hydrocarbons having 6 to 10 carbon atoms are preferable. Specific examples of the aliphatic polyisocyanate compound include 1,4,8-triisocyanatooctane, 1,4,8-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,8 6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, and the like.

  On the other hand, as a hydroxy compound having an acryloyl group or a methacryloyl group in the molecule (hereinafter referred to as “(meth) acryloyl group”), hydroxyalkyl (meth) acrylate, hydroxycycloalkyl (meth) acrylate, poly Alkylene glycol mono (meth) acrylate, adduct of glycidyl (meth) acrylate and (meth) acrylic acid, ring-opening reaction product of these (meth) acrylate compounds and ε-caprolactone, glycidyl ether and (meth) acrylic acid And adducts of phenylglycidyl ether and (meth) acrylic acid, and the like, and hydroxyalkyl (meth) acrylates and polyalkylene glycol mono (meth) acrylates are particularly preferred.

  Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, glycidol dimethacrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, etc. are available, and pentaerythritol tri (meth) acrylate is particularly preferred.

  Specific examples of the polyalkylene glycol mono (meth) acrylate include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene oxide mono (meth) acrylate, and ethylene-propylene glycol block polymer. There are adducts with (meth) acrylic acid, and polyethylene glycol mono (meth) acrylate is particularly preferred.

  By subjecting such an aliphatic polyisocyanate compound and a hydroxy compound having a (meth) acryloyl group to a urethanization reaction according to a conventional method, an ultraviolet curable paint containing an unsaturated urethane compound can be obtained. Such an ultraviolet curable paint can be used as an aqueous emulsion paint using water as a solvent. Here, “emulsion” (also called emulsion) is also called an emulsion, in which liquid particles form a milky state (dispersed system) as colloidal particles or coarser particles. Although it is meaning (Saburo Nagakura et al., “Iwanami Rikagaku Dictionary (5th edition)” page 152, published by Iwanami Shoten Co., Ltd. on February 20, 1998), it is generally used in a broader sense in this specification. The term “emulsion” shall be used as “in which solid or liquid particles are dispersed in a liquid”.

  A halogen lamp, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, the sun, or the like can be used as a light source for curing the applied ultraviolet curable paint, and a metal halide lamp having three peaks in ultraviolet intensity is particularly preferable. Transparent organic synthetic resin sheets on which UV-curable coatings are applied include PE (polyethylene) sheets, PP (polypropylene) sheets, PET (polyethylene terephthalate) sheets, acrylic resin (including methacrylic resin) sheets, vinyl chloride sheets, and polyurethane. Although there are sheets, etc., a PET sheet is particularly preferable. Moreover, it is preferable that the visibility (visible light transmittance) of a transparent organic synthetic resin sheet is 90% or more.

  Hereinafter, although the sheet | seat with a coating film which concerns on the Example of this invention is demonstrated, referring drawings, this invention is not limited at all by these Examples.

[Example 1]
First, the sheet | seat with a coating film which concerns on Example 1 of this invention is demonstrated with reference to FIG. FIG. 1 is a flowchart showing a method for producing a coated sheet according to Example 1 of the present invention. FIG. 2 is a perspective view showing the structure of the coated sheet according to Example 1 of the present invention. FIG. 3 is a perspective view showing a sheet with a coating film according to a first application example of Example 1 of the present invention. FIG. 4 is a perspective view showing a coated sheet according to a second application example of Example 1 of the present invention.

  Initially, the manufacturing method of the sheet | seat with a coating film which concerns on the present Example 1 is demonstrated with reference to FIG. As shown in FIG. 1, first, an isocyanate compound 2 and a hydroxy compound 3 which are raw materials of an unsaturated urethane compound are mixed and reacted to produce an unsaturated urethane compound solution (step S10). Here, as the isocyanate compound 2, trade name “Delanate TPA-100” manufactured by Asahi Kasei Co., Ltd., which is tris (6-isocyanatohexyl) isocyanurate, was used. In addition, as the hydroxy compound 3, a trade name “NK Ester A-TMM-3L” manufactured by Shin-Nakamura Chemical Co., Ltd., which is a mixture of tetramethylol methane triacrylate and tetramethylol methane tetraacrylate, and a polyol compound A trade name “Blemmer AE350” manufactured by Shin-Nakamura Chemical Co., Ltd. was used.

  A small amount of hydroquinone and dibutyltin laurate were added as a polymerization inhibitor and a reaction accelerator. The reaction was carried out at 80 ° C. for 8 hours, the infrared absorption (IR) spectrum of the reaction product was measured, and the reaction was terminated when the isocyanate absorption peak (2170 cm −1) disappeared. While emulsifying the unsaturated urethane compound thus obtained using a homomixer, it is gradually added to distilled water as a solvent 4 to which an emulsifier has been added so as to be 40% by weight, and an aqueous emulsion paint is obtained as an emulsion. Obtained. At this time, 2 wt% of a trade name “Darocur 1173” manufactured by Ciba Specialty Chemicals Co., Ltd. was added as an ultraviolet curing agent.

  Next, an antistatic agent for a polyester resin as an antistatic agent 5 and a thiosulfite silver complex as a silver complex antibacterial agent 6 are added to and mixed with the water-based emulsion paint, and an unsaturated polyester resin 7 is further added. By adding and mixing (step S12), the ultraviolet curable coating material 1 is manufactured.

  Here, the antistatic agent 5, the silver complex antibacterial agent 6, and the unsaturated polyester resin 7 were added so as to be 1.5% by weight with respect to 100% by weight of the ultraviolet curable paint 1, respectively. As the antistatic agent for polyester resin as the antistatic agent 5, a mixture of polyglycerin fatty acid ester and calcium silicate was used. Furthermore, the thiosulfite silver complex as the silver complex antibacterial agent 6 is prepared by dissolving silver acetate in pure water at 40 ° C. to make a saturated solution, and dissolving sodium sulfite and sodium thiosulfate sequentially in this saturated solution. did.

  The ultraviolet curable paint 1 thus manufactured is applied to a surface of a PET (polyethylene terephthalate) sheet having a thickness of 100 μm as a transparent organic synthetic resin sheet in a class 100 clean room, and a coating thickness of 8 μm. (Step S14), and heated and dried at 70 ° C. for 10 minutes to remove the solvent (Step S16), and irradiated with ultraviolet rays (UV) using a metal halide lamp having three peaks in ultraviolet intensity. By curing (Step S18), the coated sheet 10 according to Example 1 was obtained.

  Here, as a PET (polyethylene terephthalate) sheet, a trade name “Cosmo Shine (registered trademark) A4300” manufactured by Toyobo Co., Ltd. was used. This "Cosmo Shine (registered trademark) A4300" has a total light transmittance of 92.3% according to JIS K-7105, and both surfaces are subjected to easy adhesion treatment. About the sheet | seat 10 with a coating film which concerns on this Example 1 manufactured in this way, the performance covers six items of abrasion resistance property, chemical resistance, ultraviolet-ray resistance, transparency, antibacterial property, and nonflammability. evaluated.

  First, the wear resistance was evaluated by measuring the static friction coefficient and the dynamic friction coefficient. As a test method, it implemented according to JIS-K-7125, and used the sheet | seat 10 with a coating film and the PET sheet | seat which is a base material as a test body, and used the leather and the mat | matte as a partner material. The results are shown in Table 1.

  As shown in Table 1, the coated sheet 10 according to Example 1 is smaller than the PET sheet for both the static friction coefficient and the dynamic friction coefficient for the leather, and for the mat. Both the static friction coefficient and the dynamic friction coefficient are larger than those of the PET sheet. Therefore, it is clear that leather shoes have a low coefficient of friction and excellent wear resistance, and when mats are laid on them, the coefficient of friction is large and difficult to shift, and it has clearly excellent properties as a flooring. became.

  Next, the chemical resistance was tested. As a test method, about 0.1 ml of the test solution was dropped on the surface of each test specimen, using the coated sheet 10 and the PET sheet as a base material as test specimens, covered with a watch glass and left at room temperature for 24 hours. Then, the test solution was washed off while gently rubbing the surface of the specimen in running water, and after drying, the appearance change was observed. Then, the chemical resistance was evaluated in five stages of A, B, C, D, and E, with “A” indicating no change in appearance and “E” indicating that the surface was completely dissolved.

  Test liquids include hydrochloric acid (special grade, 35.0% to 37.0%), hydrofluoric acid (special grade, 46.0%), sulfuric acid (special grade, 95.0%), saturated aqueous sodium hydroxide solution (water Five chemicals, sodium oxide (special grade, 97.0% used) and 2-butanone (special grade, 99.0%) were used. The results are shown in Table 2.

  As shown in Table 2, it was revealed that the coated sheet 10 according to Example 1 shows excellent chemical resistance with no change in appearance at all for five types of chemicals. On the other hand, in the PET sheet having no coating film by the ultraviolet curable coating 1, no change in appearance was observed for hydrochloric acid, hydrofluoric acid, 2-butanone, but sulfuric acid and saturated sodium hydroxide. It was not resistant to the aqueous solution.

  Next, a test for ultraviolet resistance was performed. As a test method, it carried out according to JIS-K-6772. As a result, it became clear that the color tone of the coated sheet 10 did not change at all even when irradiated with ultraviolet rays, and had excellent ultraviolet resistance.

  Moreover, the test was done also about the visible light transmittance | permeability of the sheet | seat 10 with a coating film, and an ultraviolet-ray spectral transmittance. As a test method, a standard white plate: barium sulfate, sampling pitch: 0.5 nm, slit width: 20 nm, scan speed: medium speed using an ultraviolet-visible spectrophotometer V-570 manufactured by JASCO Corporation as a test instrument. It carried out on the condition of. As a result, the spectral transmittance of visible light (400 nm to 800 nm) was 90.6%, which was almost the same as the base PET sheet (92.3%).

  Moreover, although the spectral transmittance of ultraviolet rays (250 nm to 400 nm) was 47.1%, 84.7% of them was UV-A having a wavelength close to visible light (320 nm to 400 nm), which is harmful to human bodies and the like. Neither UV-B (280 nm to 320 nm) nor UV-C (190 nm to 280 nm) was found to transmit little.

  Next, the antibacterial property was tested. As a test method, MRSA (Methicillin resistant Staphylococcus aureus IID 1677) and Escherichia coli (Escherichia coll NBRC 3972) are used as test bacteria according to JIS-Z-2801, 5, 2, and the coated sheet 10 and the substrate Using the PET sheet, which is a material, as test specimens, the surface of each specimen was inoculated with the test bacteria, and the number of viable bacteria immediately after the inoculation was confirmed. The results are shown in Table 3.

  As shown in Table 3, the coated sheet 10 according to Example 1 has an antibacterial activity value against MRSA of greater than 2.7, an antibacterial activity value against E. coli of greater than 6.0, and excellent antibacterial properties. It became clear to have.

  Next, the nonflammability was tested. As a test method, an exothermic test was performed on the non-combustible material, and a total heat generation amount and a maximum heat generation rate for 20 minutes were measured. As a specimen, the coated sheet 10A was manufactured using a PET sheet having a thickness of 50 μm as a base material in the same manner as the above-described method for manufacturing the coated sheet 10 and the PET sheet having a thickness of 75 μm was used as the base material. A sheet 10B with a coating film was produced using the test piece, and a test was performed on specimens in which these sheets 10A and 10B with a coating film were respectively attached to a gypsum board. The results are shown in Table 4.

As shown in Table 4, the specimen using the coated sheet 10A according to Example 1 has a total calorific value of 5.9 MJ / m ² for 20 minutes and 8.0 MJ / m which is a standard for non-combustible materials. It satisfies the condition that less than m ^2, and in the maximum heat release rate is 186.2kW / m ^2, meets the criteria for noncombustible material called "time maximum heat generation rate exceeds 200 kW / m ² is less than 10 seconds." . Similarly, the specimen using the coated sheet 10B has a total heat generation value of 20 MJ / m ² for 20 minutes and satisfies the standard of non-combustible material, and the maximum heat generation rate exceeds 200 kW / m ² . The time is 4 seconds and still meets the standards for non-combustible materials.

  Further, as shown in Table 4, no through-holes or the like harmful to fire prevention were generated. Therefore, it became clear that the coated sheets 10A and 10B according to Example 1 are extremely preferable because they function as non-combustible materials even if they are attached to a floor or a wall as building materials.

  Next, application examples of the coated sheet 10 according to the first embodiment will be described with reference to FIGS. As shown in FIG. 2, the coated sheet 10 according to the first example is obtained by applying an ultraviolet curable coating 1 on the surface of a PET (polyethylene terephthalate) sheet 9 as a transparent organic synthetic resin sheet and applying ultraviolet rays. It is cured to form an ultraviolet curable coating film 8. In order to improve the applicability, in the sheet 11 with a practical coating film according to the application example of the first embodiment, as shown in FIG. 14 is covered.

  As shown in FIG. 3, the coated sheet 10 according to the application example 1 of the first embodiment is used by being attached to the front surface of the toilet 21 on the floor surface in the toilet 20. As a construction method, the release paper 14 on the back surface of the sheet 11 with a practical coating film shown in FIG. 2 may be peeled off, and the sheet 10 with a coating film may be attached to the floor surface with an adhesive 13. As a result, even if sewage splashes on the outside of the toilet bowl 21 or cleaning chemicals are spilled, the floor surface is not contaminated and is not corroded by the chemicals. Can keep. In addition, the PET sheet 9 can be colored to have a decorative role.

  As the sheet | seat 10 with a coating film which concerns on the application example 2 of a present Example 1, as FIG. 4 shows, there exists what is affixed and used for the channel | path floor surface 23 along the line 22 in a factory. Also in this case, as a construction method, the release paper 14 on the back surface of the sheet 11 with the practical coating film shown in FIG. 2 is peeled off, and the sheet 10 with the coating film is adhered to the passage floor surface 23 with the adhesive 13. . As a result, the passage floor surface 23 is protected, and it is difficult to slip, scratch, and is hardly contaminated, and the gloss is maintained for a long time. In addition, by coloring the PET sheet 9, a decorative role and a role of clearly indicating the passage can be provided.

  In this way, the coated sheet 10 according to Example 1 is excellent in hardness, transparency, friction resistance, chemical resistance, contamination resistance, and heat resistance, and does not need to be frequently polished. Furthermore, the surface gloss can be maintained, and the coated sheet is formed with a coating film having sufficient visibility and strength to withstand long-term use.

[Example 2]
Next, a sheet with a coating film according to Example 2 of the present invention will be described with reference to FIGS. FIG. 5 is a perspective view showing a structure of a sheet with a coating film according to Example 2 of the present invention. FIG. 6 is a perspective view showing a coated sheet according to a first application example of Example 2 of the present invention. FIG. 7: is a perspective view which shows the sheet | seat with a coating film concerning the 2nd application example of Example 2 of this invention.

  Also in the sheet with a coating film according to Example 2, the ultraviolet curable coating material 1 described above is used as the coating material for forming the coating film. That is, the production method of the ultraviolet curable coating material for producing the coated sheet according to the second embodiment is exactly the same as the production method of the ultraviolet curable coating material 1 described in the first embodiment.

  Moreover, also about the manufacturing method of the sheet | seat with a coating film which concerns on this Example 2, the base material which apply | coats the ultraviolet curable coating material 1 pastes a transparent organic synthetic resin sheet on the surface of a transparent organic synthetic resin sheet or a printing sheet. The manufacturing conditions are the same. That is, the UV curable coating material 1 is applied to a surface of a 100-μm thick PET sheet as a transparent organic synthetic resin sheet on the surface of a printed sheet in a class 100 clean room. This is carried out by removing the solvent by heating and drying at 70 ° C. for 10 minutes, and irradiating with ultraviolet rays (UV) using a metal halide lamp having 3 peaks in ultraviolet intensity. A sheet with a coating film according to Example 2 is obtained.

  As shown in FIG. 5, the sheet 15 with a coating film according to Example 2 is a transparent organic synthetic resin sheet on the surface of a printed sheet 12 on which characters, figures, patterns, photographs, etc. are printed. A PET sheet 9 is bonded, and an ultraviolet curable coating 1 is applied thereon, and then cured by ultraviolet curing to form an ultraviolet curable coating 8. In order to improve the applicability, in the sheet 16 with a practical coating film according to the application example of the modification, the adhesive 13 is applied to the back surface of the printing sheet 12 and the release paper 14 is used as shown in FIG. Covering.

  As the sheet | seat 15 with a coating film which concerns on the application example 1 of a present Example 2, as FIG. 6 shows, there exists what is affixed and used for the floor surface 25 in a shop. Also in this case, as a construction method, the release paper 14 on the back surface of the sheet 16 with a practical coating film shown in FIG. 5 is peeled off, and the sheet 15 with a coating film is adhered to the floor surface 25 with the adhesive 13. Thereby, since the printing surface of the printing sheet 12 can be seen through the sheet 10 with the coating film excellent in transparency, the appearance of the floor surface 25 in the store is improved, and the coating sheet 8 and the PET sheet 9 improve the appearance of the printing sheet 12. The surface is protected, it is difficult to slip and scratch, it is not easily contaminated, and the gloss is maintained for a long time.

  As the sheet 15 with a coating film according to the application example 2 of the second embodiment, as illustrated in FIG. 7, there is a sheet that is used by being attached to a floor 27 of a concourse of a station. Also in this case, as a construction method, the release paper 14 on the back surface of the sheet 16 with the practical coating film shown in FIG. 5 is peeled off, and the sheet 15 with the coating film is adhered to the floor surface 27 with the adhesive 13. As a result, since the printing surface of the printing sheet 12 can be seen through the coated film 10 having excellent transparency, the surface of the printing sheet 12 is protected by the coating film 8 and the PET sheet 9 while functioning as an easy-to-see guidance display board. In addition, it is difficult to slip, scratch, and is not easily contaminated, and the gloss is maintained for a long time.

  In this way, the coated film sheet 15 according to Example 2 is excellent in hardness, transparency, friction resistance, chemical resistance, contamination resistance, and heat resistance, and does not frequently undergo polishing work. However, the gloss of the surface can be maintained, and a coating film having sufficient visibility of the printing surface and strength that can withstand long-term use can be formed.

  In each of the above embodiments, the case where a PET (polyethylene terephthalate) sheet 9 is used as a transparent organic synthetic resin sheet has been described. However, the present invention is not limited to this, and other transparent organic synthetic resin sheets, for example, PE ( Polyethylene) sheets, PP (polypropylene) sheets, acrylic resin (including methacrylic resin) sheets, vinyl chloride sheets, polyurethane sheets, and the like can also be used.

  Moreover, in each said Example, although the case where the sheets 10 and 15 with a coating film were affixed on the floor surface was demonstrated, the sheets 10 and 15 with a coating film can also be affixed on other surfaces, such as a wall surface. It can also be used for decoration, advertising, etc. by hanging from the ceiling.

  Furthermore, in each said Example, although the sheet | seats 11 and 16 with a practical coating film provided with the adhesive agent 13 and the release paper 14 on the back surface of the sheet | seats 10 and 15 with a coating film were demonstrated, It is also possible to manufacture and apply an adhesive or the like on the back surface during construction.

  The configuration, shape, quantity, material, thickness, thickness, size, manufacturing method, manufacturing conditions, and the like of the other parts of the sheet with the coating film are not limited to the above embodiments. Note that the numerical values given in the examples of the present invention are not all critical values, and certain numerical values indicate preferred values suitable for implementation. It does not deny implementation.

DESCRIPTION OF SYMBOLS 1 Ultraviolet curable coating material 2 Isocyanate compound 3 Hydroxy compound 5 Antistatic agent 6 Silver complex antibacterial agent 7 Unsaturated polyester resin 8 Coating film 9 Transparent organic synthetic resin sheet 10,15 Sheet 12 with coating film Printing sheet

Claims (6)

A transparent organic synthetic resin comprising an unsaturated urethane compound containing an isocyanate compound and a hydroxy compound as a raw material compound, and at least one of the raw material compounds containing an unsaturated urethane compound having an unsaturated bond. A coated sheet formed on the sheet,
In the ultraviolet curable paint, at least one of the unsaturated urethane compounds has a polyalkyleneoxy group, and the content of the polyalkyleneoxy group is used in the unsaturated urethane compound. The isocyanate compound and the hydroxy compound The total number of moles of the raw materials having unsaturated bonds in the range of 2 to 16% by weight with respect to the total amount of The value obtained by dividing the sum of the product and the number of isocyanate groups of the isocyanate compound is in the range of 6 to 9, or the total number of moles of raw materials having an unsaturated bond The value obtained by multiplying the sum of the number of moles of the raw material having an unsaturated bond by the number of unsaturated bonds and the number of hydroxyl groups of the hydroxy compound is within the range of 6-9. And an antistatic agent in the range of 0.5% to 3% by weight and a silver complex antibacterial agent in the range of 0.5% to 3% by weight in 100% by weight of the ultraviolet curable paint. , An ultraviolet curable paint containing an unsaturated polyester resin in the range of 0.5 wt% to 3 wt%,
The UV curable paint is applied on the transparent organic synthetic resin sheet in a clean room excellent in class 1000 or more so that the coating thickness is within the range of 8 μm ± 1 μm and cured by UV curing. A coating film characterized in that the surface of the transparent organic synthetic resin sheet is subjected to easy adhesion treatment and the coating film has a visibility (visible light transmittance) of 90% or more. With sheet. A transparent organic synthetic resin sheet is pasted on the surface of a printed sheet printed on the surface, and an unsaturated urethane compound containing an isocyanate compound and a hydroxy compound as a raw material compound is contained on the transparent organic synthetic resin sheet, It is a sheet with a coating film formed by applying an ultraviolet curable paint containing an unsaturated urethane compound in which at least one of the raw material compounds has an unsaturated bond,
In the ultraviolet curable paint, at least one of the unsaturated urethane compounds has a polyalkyleneoxy group, and the content of the polyalkyleneoxy group is used in the unsaturated urethane compound. The isocyanate compound and the hydroxy compound The total number of moles of the raw materials having unsaturated bonds in the range of 2 to 16% by weight with respect to the total amount of The value obtained by dividing the sum of the product and the number of isocyanate groups of the isocyanate compound is in the range of 6 to 9, or the total number of moles of raw materials having an unsaturated bond The value obtained by multiplying the sum of the number of moles of the raw material having an unsaturated bond by the number of unsaturated bonds and the number of hydroxyl groups of the hydroxy compound is within the range of 6-9. And an antistatic agent in the range of 0.5% to 3% by weight and a silver complex antibacterial agent in the range of 0.5% to 3% by weight in 100% by weight of the ultraviolet curable paint. , An ultraviolet curable paint containing an unsaturated polyester resin in the range of 0.5 wt% to 3 wt%,
The UV curable paint is applied on the transparent organic synthetic resin sheet in a clean room excellent in class 1000 or more so that the coating thickness is within the range of 8 μm ± 1 μm and cured by UV curing. A coating film characterized in that the surface of the transparent organic synthetic resin sheet is subjected to easy adhesion treatment and the coating film has a visibility (visible light transmittance) of 90% or more. With sheet.   The coated sheet according to claim 1, wherein the surface smoothness of the coating film is an optical level of smoothness.   4. The coated film according to claim 1, wherein the transparent organic synthetic resin sheet is a PET (polyethylene terephthalate) sheet having a thickness in a range of 25 μm to 200 μm. Sheet.   The sheet with a coating film according to any one of claims 1 to 4, wherein the antistatic agent comprises an antistatic agent for a polyester resin.   The sheet with a coating film according to any one of claims 1 to 5, wherein the silver complex antibacterial agent comprises a thiosulfite silver complex.

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